Composition of polyarylenesulfide, epoxy resin and oxazoline polymer

ABSTRACT

A resin composition applicable to semiconductor or electric devices comprises (A) a polyarylenesulfide resin, (B) a bisphenol epoxy resin, (C) an oxazoline group-containing amorphous polymer, and (D) an impact resistance-improving resin which is either (d1) an acid or epoxy groups-containing vinyl polymer, or (d2) an acid or epoxy groups-containing gum polymer.

BACKGROUND ART

1. Field of the Invention

The present application relates to polyarylenesulfide resin compositionshaving a dramatically improved adhesiveness with regard to a cured epoxyresin, while retaining characteristic properties of polyarylenesulfideresins such as heat resistance and chemical resistance, and relatespractically to useful polyarylenesulfide resin compositions in a widerange of industrial fields, such as an ignition coil case for cars usedby sealing the ignition coil in the coil case made of thepolyarylenesulfide resin with an epoxy resin composition; and a coilcase in a so-called “distributorless ignition system (hereinafter,abbreviated as “DLI”) which is produced by integrating the plug and anignition coil; and furthermore relates to electric and electroniccomponents such as epoxy resin sealed type semiconductor devices.

2. Background Art

Recently, polyarylenesulfide (hereinafter, abbreviated as “PAS”) hasattracted attention as an excellent engineering, plastic having superiorheat and chemical resistances.

One of the application fields of the PAS resin utilizing these featuresis producing various electronic and electric components by sealingvarious electronic and electric elements in casings made of the PASresin composition formed in advance by injection molding. That is, inorder to develop a new technique for producing electronic and electriccomponents (especially, ignition coils for DLI), semiconductor elementsor coils are first mounted in a casing made of PAS resin, uncured epoxyresin is poured in the casing for sealing these elements or coils, andthe epoxy resin is finally cured by, for example, heat treatment forsealing these semiconductor elements or coils into the casing.

When the PAS resin is used for such applications, it is necessary forthe PAS resin products to be provided with a superior long-termadhesiveness to the epoxy resin at wide ranges of usage temperatures, inaddition to the intrinsic characteristics such as long-term heat andchemical resistance properties. Practically, it is required that the PASresin products sealed by epoxy resin do not peel off from the epoxysealant, even when the PAS resin products sealed by epoxy resin isrepeatedly used in a temperature range of −40° C. to 140° C. As a matterof fact, since the PAS resin is intrinsically interior in adhesivenessto epoxy resin, and the adhesion is weak even if it is reinforced byglass fibers or the like, the PAS resin has been considered not suitablefor use for sealing applications with epoxy resins.

In order to improve the adhesion of the PAS resin with the epoxy resin,Japanese Patent Application. First Publication No. Hei 9-3326, disclosesa technique for improving the adhesion by addition ofα-olefine/α,β-unsaturated carboxylic acid glycidylester copolymer and anamide carboxylic acid-type wax to the PAS resin for relieving stresscaused at an interface between the PAS resin and the epoxy resin at thetime of heating and cooling.

However, the PAS resin composition disclosed in Japanese PatentApplication, First Publication No. Hei 9-3326, does not exhibit asatisfactory adhesiveness with the epoxy resin and generation of cracksare observed in the heating and cooling cycles, which means thatconventional PAS resins are not sufficient to satisfy the level forpractical use.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a PASresin which has an dramatically improved adhesion strength with theepoxy resin during heating and cooling operations, while retaining itsintrinsic superior heat and chemical resistances, and which has animproved crack resistance in heating and cooling cycles by incorporatinga resin for improving the impact resistance.

The inventors of the present invention have carried out a series ofstudies for solving the above problems, and they have completed thepresent invention by discovering that the adhesiveness of the PAS resincan be dramatically improved by incorporating a bisphenol-type epoxyresin and an oxazoline-group-containing amorphous polymer, and that asuperior crack resistance can be additionally provided to the PAS resinby incorporating a bisphenol-type epoxy resin, anoxazoline-group-containing copolymer, and an impact resistance improvingresin.

That is, the present invention relates to a polyarylenesulfide resincomposition, wherein the polyarylenesulfide composition essentiallycontains polyarylenesulfide resin (A), bisphenol-type epoxy resin (B),and oxazoline-group-containing amorphous polymer (C).

Although there is not particular limitation on polyarylenesulfide resin(A), it is preferable for the polyarylenesulfide (A) to have repetitivestructural units expressed by a general formula 1 [—Ar—S—] (in theformula, —Ar— represents divalent aromatic group including at least onesix-membered ring of carbon) as the main structural units, and it ismore preferable for the polyarylenesulfide to contain more than 70 mol %of such structural units shown in the general formula 1 from the pointof view of heat and chemical resistances.

Among polyarylenesulfide compositions containing more than 70 mol % ofstructural units expressed by the general formula 1, polyphenylenesulfide (hereinafter, abbreviated as “PPS”) containing repetitivestructural units expressed by the general formula 2 [-φ-S—] ispreferable, and it is particularly preferable for a polymer to containmore than 70 mol % respective structural units expressed by the generalformula 2 from the point of view of high mechanical strength which is acharacteristic property for a crystalline polymer and also from point ofview of toughness and the chemical resistance.

Examples of copolymer components having the structural unit in thepolyarylenesulfide resin (A) expressed by the general formula 1 includecouplings such as a metha-coupling, ether-coupling, sulfonic-,sulfonic-coupling, sulfideketone-coupling, biphenyl-coupling,substituted phenylsulfide-coupling, biphenyl-coupling, substitutedphenylsulfide coupling, tri-functional phenylsulfide, and naphtylcoupling, which are illustrated below by chemical formulas 2 to 10. Thecontent of the copolymer component is preferably less than 30 mol %,but, when a coupling more than a tri-functional coupling is included,the content is preferably less than 5 mol %, more preferably less than 3mol %.

(in the formula, R represents an alkyl group, a nitro group, a phenylgroup or a alcoxy group)

It is noted that the polyarylenesulfide resin (A) used in the presentinvention has a superior reactivity with the (B) or (C) components asuperior compatibility with the (B) and (C) (here, compatibility means acapability of being smaller particles size of the component (B), (C) or(D)), and the resin (A) is capable of providing the high adhesivenesswith the epoxy resin. From the point of view of the above superiorreactivity of the (B) and (C) components and high adhesiveness to thecured epoxy resin, it is preferable for the polyarylenesulfide resin toprovide the following properties; ΔHCl is not more than 10 μmol/g, ΔNaOHis within 5 to 30 μmol/g, and (ΔNaOH-ΔHCl) ≧5 μmol/g.

Here, ΔHCl, ΔNaOH, and (ΔNaOH-ΔHCl) are obtained by the followingmeasurements.

10 g of polyarylenesulfide resin (A) is stirred after adding 10 mol of 1mol/l of HCl, and the suspension is filtrated. The separated solid isrepeatedly washed by water until the HCl is not detected, and all offiltrate used for washing is collected and HCl in the collected filtrateis titrated by NaOH, and the molar number of HCl is defined as ΔHCl.

Next, the polyarylenesulfide resin (A) after washing by water is againdispersed in distilled water and stirred after adding 10 ml of 1 mol/lof NaOH. The solution is filtrated after stirring, and the filtratedsolid is repeatedly washed by water until NaOH is not detected. All thefiltrate used for washing is collected and NaOH in the filtrate istitrated by HCl, and the molar number of NaOH is defined as ΔNaOH. The(ΔNaOH-ΔHCl) is a difference between ΔNaOH and ΔHCl.

It is preferable that the concentration of the terminal thiol groups ofthe polyarylenesulfide resin (A) is within a range of 5 to 50 μmol/g inorder to provide the resin (A) with a superior reactivity with thecomponents (B) and (C), a good compatibility, a superior processability,and a good flowability. That is, when the concentration increases to 5μmol/g, the dispersion ability increases, and when the concentrationdecreases below less than 50 μmol/g or more than 5 μmol/g, theflowability becomes superior.

The concentration of the terminal thiol groups is obtained by theiodoacetamide method. The iodoacetamide method is carried out by thesteps of acidifying the PAS resin by an acid such as hydrochloride forconverting into thiol groups and subsequently generating the iodine bythe reaction of iodoacetamide with all of the terminal thiol groups byheating; while the concentration of the terminal thiol groups present inthe PAS resin at the initial stage is obtained by calculating the molarnumber of acid consumed for acidification and the molar number of iodinedetermined by UV spectrometry.

In more detail, the practical procedures of the measurement are asfollows.

10 mg to 1 g of the powdered PAS resin sample is weighed, after theweighed sample is put into a sealed test tube, 1 ml of acetone and 3 mlof pure water are added, and stirred after further addition of dilutedhydrochloride. After stirring, a filtrate by filtration is back titratedby use of NaOH solution for obtaining the molar number of thehydrochloride consumed for terminal acidification. Subsequently, afterbeing separated by filtration, the polymer sample is washed by purewater for 30 minutes, 2.5 ml of acetone solution consisting of 2.5 ml ofacetone and 50 mmol of iodoacetamide is added, seal by a stopper, heatedat 100° C. for 60 minutes, the water is cooled and the seal is opened,the liquid phase is separated, and absorbance at 450 nm (absorbance at12) is measured by the ultraviolet light absorption spectrometer. Theconcentration of the whole terminal thiol groups is calculated by theuse of a calibration curve produced in advance for model thiol compounds“C1-C6H4-SH” (it is preferable to select a sample amount such that theconcentration of the thiol compound in the actone slurry falls within arange of 0.1 to 0.3 mmol). The molar number obtained by subtracting themolar number of hydrochloride consumed for terminal acidification fromthe whole terminal thiol groups is the concentration of the terminalthiol groups of the PAS resin. The average concentration of the terminalthiol groups for the same powdered sample is obtained by taking threemeasurements.

Any molecular structures of the polyarylenesulfide resin (A) may used inthe present invention whether the molecules are substantially linearstructure without having branching or bridging structures, or themolecules having branching or bridging structures, the resin (A) havinga linear molecular structure is preferable from the points of view ofreactivity and compatibility.

Although there is not particular limitation in the polymerization methodof such a polyarylenesulfide resin (A), certain polymerization methodsare preferable, including a nucleophilic displacement method such as amethod {circle around (1)} by a reaction of a halogen substitutedaromatic compound with an alkali sulfide. Some practical examples of theabove method {circle around (1)} include:

{circle around (1)}-1: a method of polymerizing p-dichlorobenzene underpresence of sulfur and sodium carbonate;

{circle around (1)}-2: a method of reacting p-dichlorobenzene withsodium sulfide in a polar solvent;

{circle around (1)}-3: a method of reacting p-dichlorobenzene withsodium hydrogensulfide and sodium hydroxide in a polar solvent: and

{circle around (1)}-4: a method of reacting p-dichlorobenzene withhydrogen sulfide and sodium hydroxide in a polar solvent.

Furthermore, another method {circle around (2)}, consists ofself-condensation of the thiophenols such as p-chlorothiophenol underco-presence of alkali catalysts such as potassium carbonate or sodiumcarbonate and a copper salt such as copper iodite. Examples of polarsolvents used in the method {circle around (1)} include amide-typesolvents such as N-methylpyrrolidone, dimethylacetoamide, and sulfolane.

The other polymerization method is an electrophilic substitutionreaction constituting a method {circle around (3)} which is acondensation polymerization of aromatic compounds such as benzen withsulfur chloride under presence of a catalyst of a Lewis acid catalyst bya Fridel-Crafts reaction.

Among these polymerization methods, the preferable one is {circle around(1)}-2, since this method allows yielding a polyarylenesulfide resinhaving a large molecular weight and also allows obtaining a highpolymerization yield.

Practically, the most preferable method is to react p-dichlorobenzenewith sodium sulfide in amide-type solvents such as N-methylpyrrolidoneor dimethylacetamide; and in sulfone-type solvents such as sulfolane. Itis also preferable to add alkaline metal salts of carboxylic acid andsulfonic acid, or alkali hydroxide in order to control the degree ofpolymerization.

As described above, it is preferable for the polyarylenesulfide resin(A) to have a substantially linear structure from points of view ofreactivity and compatibility. Although there is not particularlimitation, examples of methods of producing the polyarylenesulfideresin having a substantially linear structure include reactingalkali-metal sulfide and organic alkali metal carboxylates such asdihalo-aromatic compounds and lithium acetate in an amide-type solventsuch as N-methylpyrrolidone and dimethylacetamide, and a water-additiontwo stage polymerization method to add a large amount of water andincrease the polymerization temperature of the reaction system duringthe polymerization reaction of the dihalo-aromatic compound with analkaline metal sulfide in an organic amide-type solvent.

Particularly, the polyarylenesulfide resin (A) having a substantiallylinear structure suitable for the present invention is preferably usedafter being subjected to acid treatment and washing.

Although there is no limitation for acids for the acid treatment if theacid does not decompose the polyarylenesulfide resin (A), examples ofacids used for the acid treatment include acetic acid, hydrochloride,sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propylacid. Among these, acetic acid and hydrochloride are preferably used.The methods of acid treatment include immersion of thepolyarylenesulfide resin (A) in the acid or acid solution. Stirring orheating may be added during immersion if necessary. The acid treatmentis carried out sufficiently in acetic acid by immersing the PAS resin inthe acetic acid solution of pH4 heated at temperatures in a range of 80to 90° C. for 30 minutes. The PAS resin after the acid treatment iswashed by water or warm water several times in order to physicallyremove the remaining acid or salt. The water used for washing ispreferably distilled water or deionized water.

The polyarylenesulfide resin (A) to be used for the acid treatment maybe in the form of a power or in the form of a slurry obtainedimmediately after polymerization.

The bisphenol-type epoxy resin (B) is an essential component fordramatically improving the adhesion of the PAS resin to the cured epoxyresin, and the bisphenol-type epoxy resin (B) is also useful indramatically improving compatibility of the impact resistant component(D), when that component (D), which will be described in the latersection, is also used.

As bisphenol-type epoxy resin (B), any type of the bisphenol-type epoxyresins may be used, without any limitation, including bisphenol A-typeepoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxyresin, and bisphenol AD-type epoxy resin; and in the present invention,bisphenol A-type is most preferable because it greatly enhances theadhesiveness to the cured epoxy resin.

Examples of the practical bisphenol A-type epoxy resins includeglycidylether of bisphenol A, and a compound in which glycidylether isconverted into high molecular weight by use of bisphenol A.

It is preferable for bisphenol-type epoxy resin (B) to have an epoxyequivalent within a range of 150 to 2100 g/eq. The range of 700 to 2100g/eq is more preferable for the resin (B) composition for providingbetter processability and better compatibility.

The oxazoline-group-containing amorphous polymer (C), used as one of theessential components in the present invention, is useful, similar to theabove described (B) component, for dramatically improving theadhesiveness of the cured epoxy resin and also useful for improving thecompatibility of the impact resistance improving resin (D) in the PASresin. That is, in the present invention, the PAS resin exhibits anunusual superior adhesion capability to the cured epoxy resin by use ofthe (B) component and the (C) component together. Theoxazoline-group-containing amorphous polymer (C) is quite effective forfine dispersion of the impact resistance improving resin (D) in the PASresin and for improving the thermal shock resistance of the resincomposition product as a whole.

Here, the oxazoline-group-containing amorphous polymer (C) is thepolymer which is in an solidified state by cooling from a highertemperature range than the transition temperature or the melting, point,and which contains an amorphous structure of more than 80 wt % attemperature region below 200° C.

Practically, examples of the oxazoline-group-containing amorphouspolymer (C) include a homopolymerization of oxazolinyl group containingpolymerizable unsaturated monomer and a copolymer of said monomer andthe other polymerizable unsaturated monomers.

A preferable example of the oxazolinyl group containing polymerizableunsaturated monomer is vinyloxazoline. Examples of the otherpolymerizable unsaturated monomers which are co-polymerizable with theoxazolinyl group containing polymerizable unsaturated monomer includearomatic vinyls such as styrene; vinyl cyanides or vinyl acetates suchas acrylonitrile; unsaturated carboxylic acids or its derivatives suchas (meth)acrylate, (meth)acrylate ester, maleic acid anhydride; anddiene components such as α-olefin, butadiene, and isoprene. Among theseexamples, styrene and acrylonitrile are preferable from the point ofview of compatibility.

The copolymers of the oxazolinyl group containing polymerizableunsaturated monomer and the other polymerizable unsaturated monomer ispreferably a binary or ternary copolymer selected from the above monomercomponents, and practically a combination of vinyloxazoline and styreneand/or acrylonitrile is preferable.

In the present invention, addition of the impact resistance improvingresin (D) in addition to the above (A) to (C) components dramaticallyimproves the toughness of the formed products, the adhesiveness to thecured epoxy resin, and, as described above, the crack resistanceproperty by thermal shock cycles.

Although there is no limitation in selecting the impact resistanceimproving resin (D), it is preferable to use vinyl-type polymers (d1)containing acid- or epoxy-group and a gum polymer (d2) containing anacid- or epoxy group in order to improve the crack resistance property.

Although there is no particular limitation, preferable examples of thevinyl-type polymers (d1) containing acid- or epoxy-group includeα-polyolefin (d1-1) containing acid- or epoxy-group or α,β-unsaturatedcarboxylic acid alkylester polymer (d1-2) containing acid- orepoxy-group.

Although there is no particular limitation, examples of the α-polyolefin(d1-1) containing acid- or epoxy-group include copolymers of α-olefin,and α,β-unsaturated carboxylic acids or their anhydrides; copolymers ofα-olefin, and α,β-unsaturated carboxylic acids or their anhydrides, andα,β-unsaturated alkylester carboxylates; copolymers of α-olefines,α,β-unsaturated glycidylester carboxylates; and copolymers of α-olefins,α,β-unsaturated glycidylester carboxylates, and α,β-unsaturatedalkylester carboxylates.

Here, examples of α-olefin include ethylene, propylene, butene-1,pentene-1, hexene-1, heptene-1,3-methylbutene-1,4-methylpentene-1, andtheir combinations, but the preferable example is ethylene.

Examples of α,β-unsaturated carboxylic acids or their anhydrides includeacrylic acid, methacrylic acid, crytonic acid, maleic acid, fumaricacid, itaconic acid, citraconic acid, butanedicarboxylic acid and theiranhydrides, and maleic anhydride and succinic anhydride are the mostpreferable examples.

Examples of α,β-unsaturated glycidylester carboxylates includeglycidylacrylate, glycidylmethacrylate, glycidylethacrylate, and thepreferable example is glycidylmethacrylate.

Examples of α,β-unsaturated alkylester carboxylates include unsaturatedcarboxylic acids of 3 to 8 carbon atoms such as alkylesters includingacrylic acid, methacrylic acid, and ethacrylic acid; and practicalexamples include methylacrylate, ethylacrylate, n-propylacrylate,isopropylacrylate, n-butylacrylate, t-butylacrylate, isobutylacrylate,methylmethacrylate, ethylmethacrylate, n-propylmethacrylate,isopropylmethacrylate, n-butylmethacrylate, t-butylmethacrylate,isobutylmethacrylate, and preferable examples are methylacrylate,ethylacrylate, and n-butylacrylate.

In α,β-unsaturated carboxylic acids or their anhydrides, although thereis no particular limitation, a denaturation ratio of each monomercomponent for α-olefin is not more than 10 wt %, preferably in a rangeof 0.1 to 5 wt % for a unit weight of copolymer, when the denaturatedportion is converted as the weight of the monomer in the copolymer. Whenα,β-unsaturated alkylester carboxylate is additionally used, thepreferable range changes into 5 to 35 wt %.

The α,β-unsaturated alkylester carboxylate polymers (d1-2) containingacid- or epoxy-group have a structure in which the acid-group or epoxygroup is introduced into the α,β-unsaturated alkylester carboxylatepolymer, and the practical example is a compound obtained byco-polymerization of α,β-unsaturated carboxylic acid or its anhydride,or α,β-unsaturated glycidylester carboxylate or its anhydride withα,β-unsaturated alkylester carboxylates.

Any examples of the above described α,β-unsaturated alkylestercarboxylates may be used in the present invention, and the practicalexamples is a carboxylic acid of 3 to 8 carbon atoms including acrylatessuch as methylacrylate, ethylacrylate, n-propylacrylate,isopropylacrylate, n-butylacrylate, t-butylacrylate, isobutylacrylate,methylmethacrylate, ethylmethacrylate, n-propylmethacrylate,isopropylmethacrylate, n-butylmethacrylate, t-butylmethacrylate, andisobutylacrylate; and they may be used alone or in combination. Amongthese compounds, the most preferable examples include methylacrylate,ethylacrylate, and n-butylacrylate.

Examples of α,β-unsaturated carboxylic acids or their anhydrides forco-polymerizing with α,β-unsaturated alkylester carboxylates includeacrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleicacid, fumaric acid, itacoic acid, citraconic acid, butenedicarboxylicacid and their anhydrides; and preferable examples are maleic anhydrideand succinic anhydride.

Practical examples of α,β-unsaturated glycidylester carboxylates forcopolymerizing with α,β-unsaturated alkylester carboxylates includeglycidylacrylate, glycidylmethacrylate, and glycidylethacrylate; andglycidylmethacrylate is preferably used.

When structural units in a copolymer are converted into an weight ratioof a monomer, the denaturation ratio of α,β-unsaturated carboxylic acidsand their anhydrides is within a range of 0.01 to 10 wt %., morepreferably in a range of 0.05 to 5 wt % for a unit weight of thecopolymer. The denaturation ratio of α,β-unsaturated glycidylestercarboxylates used for co-polymerizing with α,β-unsaturated alkylestercarboxylates is preferably in a range of 0.1 to 15 wt %, and morepreferably in a range of 5 to 10 wt % per a unit weight of thecopolymer.

Hereinafter, a gum-type polymer (d2) containing acid- or epoxy-group isdescribed. Although there is not particular limitation, the gum-typepolymer (d2) containing acid- or epoxy-group is preferably ahydrogenated copolymer containing acid- or epoxy-group of conjugateddienes and aromatic vinyl monomers. A practical example is a compoundobtained by graft co-polymerization of hydrogenated copolymer ofconjugated dienes and aromatic vinyl monomers with α,β-unsaturatedcarboxylic acids or their anhydrides or α,β-unsaturated glycidylestercarboxylates.

The hydrogenated copolymers of the conjugated dienes and the aromaticvinyl hydrocarbons are defined as a block copolymer or a randomcopolymer of conjugated dienes and aromatic vinyl hydrocarbons and atleast 80% of the copolymer is reduced by hydrogenation. In the presentinvention, a block copolymer of conjugated dienes and aromatic vinylhydrocarbons are preferably used. It is noted that the unsaturated bondswhich are reduced by hydrogenation do not include double bonds ofaromatic nucleus.

Examples of conjugated dienes include 1,3-butadiene, isoprene,1,3-pentadiene, and among conjugated dienes, 1,3-butadiene and isopreneare preferable.

Examples of aromatic vinyl hydrocarbons include styrene,α-methylstyrene, o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene,and vinylnaphthalene; and styrene is the most preferable.

Practical examples of the hydrogenated copolymer of the conjugateddienes and the aromatic vinyl hydrocarbons include tri-blockhydrogenated copolymer of styrene/butadiene/styrene and tri-blockhydrogenated copolymer of styrene/isoprene/styrene, and tri-blockhydrogenated copolymer of styrene/butadiene/styrene is preferable fromthe point of view of an excellent crack resistance property.

Examples of α,β-unsaturated carboxylic acids or their anhydrides usedfor graft co-polymerization with the hydrogenated copolymers shown indetail include acrylic acid, methacrylic acid, ethacrylic acid, clitonicacid, maleic acid, fumaric acid, itacoic acid, citracoic acid,butenedicarboxylic acid and their anhydrides; and preferable examplesare maleic anhydride and succinic anhydride.

Practical examples of α,β-unsaturated glycidylcarboxylates includeglycidylacrylate, glycidylmethacrylate, and glycidylethacrylate, andglycidylmethacrylate is particularly preferable.

Although there is not particular limitation, the content of theacid-group or the epoxy-group in the hydrogenated compounds (d2) ispreferably in a range of 0.01 to 10 wt %, and more preferably in a rangeof 0.05 to 5 wt %, for the α,β-unsaturated carboxylic acids or theiranhydrides; and preferably 0.1 to 15 wt %, and more preferably in arange of 0.5 to 10 wt %, when the content of the functional groups iscalculated as the content of monomers in the raw material.

Among two compounds including the vinyl-type polymers (d1) containingacid- or epoxy-group and the gum-type polymers (d2) containing acid- orepoxy-group, compounds containing an acid-group are preferable for theirexcellent adhesiveness to the cured epoxy and superior crack resistanceproperty, and these properties become remarkable and it is preferable touse the acid-group containing vinyl-type polymers (d1), and acid-groupcontaining α-olefin (d1-1) is more preferable, and copolymers ofα-olefin, α,β-unsaturated carboxylic acids or their anhydrides, andα,β-unsaturated alkylester carboxylate are the most preferable.

Although the percentage content of the above described respectivecomponents in the composition of the present invention is not limited,preferable percentage contents of the polyarylenesulfide resin (A) is ina range of 30 to 90 wt %, that of bisphenol A-type epoxy resin (B) is ina range of 1 to 10 wt %, and that of oxazoline-group-containing polymer(C) is in a range of 1 to 20 wt % in order to yield remarkable effects.When the impact resistance improving component (D) is used together forimproving the crack resistance property the percentage content of thecomponent (D) is preferably in a range of 0.5 to 20 wt %.

In the present invention, it is further preferable to incorporatefibrous reinforcing materials (L) in addition to the above described (A)to (C) or to (A) to (D).

The fibrous reinforcing materials are not particularly limited, if theyattain the object of the present invention. Practical examples offibrous reinforcing materials include glass fiber, carbon fiber, zincoxide fiber, asbestos fibers silica fiber, aluminum borate whisker,silica-alumina fiber, zirconia fiber, boron nitride fiber, siliconnitride fiber, potassium titanate fiber, inorganic fibrous materialssuch as metallic fibrous materials of stainless steel, aluminum,titanium, copper and brass; and high melting point organic fibrousmaterials such as aramid fiber, fibrous materials of polyamide,fluororesin, and acryl resins; and glass fiber is generally preferable.

Although the content of the fibrous material is not limited, a range of5 to 50 wt % in the resin composition is a preferable range.

The fibrous reinforcing materials may be used for improving the crackresistance property against the thermal shock, and the PAS resin isreinforced to withstand the stress due to its own expansion andcontraction such that the generation of crack is further suppressed.

The compatibilities of the PAS resin (A) with theoxazoline-group-containing polymer (C) and with the impact resistanceimproving resin (D) are further improved by incorporating silanecompounds (F). Particularly, the silane compounds are effective in aminute dispersion of the impact resistance improving resin (D) such thatthe impact resistance of the resin composition can be drasticalyimproved.

Any silane coupling agents containing organic functional groups andsilicon atoms in the molecular structure may be used as such silanecompounds (F). Preferable examples of silane compounds (F) includealkoxysilane or phenoxysilane containing epoxy-group, alkoxysilane orphenoxysilane containing amino-group, and alkoxysilane or phenoxysilanecontaining isocyanate-group. These compounds may be used alone or incombinations of two or more.

It is preferable for epoxyalkoxysilane or epoxyphenoxysilane to havemore than one epoxy group and to have two or three alkoxy- orphenoxy-groups; and examples of such silane compounds includeγ-glycidoxypropyltriphenoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, andγ-glycidoxypropyltriethoxysilane.

It is preferable for aminoalkoxysilane or aminophenoxysilane to havemore than one amino group and to have two or three alkoxy- orphenoxy-groups in one molecule; and examples of such silane compoundsinclude γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropyltriphenoxysilane, γ-aminopropylmethyldiethoxysilane,γ-aminopropylmethyldimethoxysilane,N-β-(aminoethyl)-γ-aminopropyltriethoxysilane,N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,N-γ-(aminoethyl)-γ-aminopropylmethyldiethoxysilane,N-γ-(aminoethyl)-γ-aminopropylmethyldimethoxysilane,N-phenyl-γ-aminopropyltriethoxysilane, andN-phenyl-γ-aminopropyltrimethoxysilane.

It is preferable for isocyanatealkoxysilane or isocyanatephenoxysilaneto have more than one isocyanate group and to have two or three alkoxy-or phenoxy-groups in one molecule; and examples of such silane compoundsinclude isocyanatepropyltriethoxysilane,isocyanatepropyltriphenoxysilane, isocyanatepropyltrimethoxysilane, andisocyanatepropylmethyldiethoxysilane.

It is preferable to add the silane compound (F) in the present resincomposition in a range of 0.01 to 3.0 wt %.

Further addition of the ester of the higher fatty acid of polyhydricalcohol (G) is useful for improving the mold lubrication of the resinand is also useful for further improving the adhesiveness of the resinproducts with the cured epoxy resin.

Here, the preferable polyhydric alcohol includes alcohol having morethan two hydroxy-groups, and the preferable higher fatty acid includessaturated or unsaturated fatty acids of 8 to 45 carbon atoms.

Practical examples of esters of higher fatty acid of polyhydric alcoholinclude fatty acids such as caprylic acid, lauric acid, myristic acid,behenic acid, stearic acid, montanic acid, oleic acid, and palmiticacid; and esters of polyhydric alcohol and its branched polyesteroligomer such as ethyleneglycol, glycerin, 2-methylpropane-1,2,3-triol,and pentaerythritol.

It is preferable to add the ester of the higher fatty acid of polyhydricalcohol (F) in a range of 0.01 to 3.0 wt % for the total amount of theresin composition.

From the point of view of improving the resistance against thermaldecomposition of the PAS resin due to the high forming temperaturepreferable examples of the compound (G) include ethyleneglycol,2-methyl-1,2,3-triol, ester of montanic acid of pentaerythritol and itsbranched polyester oligomer.

The resin composition of the present invention may use inorganic fillerswithin a scope not contrary to the object. Examples of inorganic fillersinclude silicon carbide, boron nitride, various metal powders, bariumsulfate, calcium sulfate, kaoline, clay, pyrophillite, bentonite,sericite, zeolite, mica, nephelincinite, talc, adalpaljite,wallastonite, PMF, ferrite, aluminium silicate, calcium silicate,calcium carbonate, magnesium carbonate, dolomite, antimony trioxide,zinc oxide, titanium oxide, alumina, magnesium oxide, magnesiumhydroxide, iron oxide, molybdenum disulfide, graphite, gypsum, glassbeads, glass powder, glass balloon, quartz, silica, and fused silica.

It is possible to add the other polymers to the present resincomposition if they are effective in improving the resin products of thepresent invention. Examples of the other polymers include homopolymersor copolymers of monomers such as ethylene, butylene, pentene, isoprene,chloroprene, styrene, α-methylstyrene, vinylacetate, vinylchloride,acrylate ester, methacrlate ester, and (meth)acrylonitrile;homopolymers, random copolymer, block copolymer, or graft copolymer ofmonomers of polyesters such as polyurethane, polybutyleneterephthalate;polyacetal, polycarbonate, polyamide, polysulfone, polyallylsulfone,polyethersulfone, polyallylate, polyphenylleneoxide, polyetherketone,polyetheretherketone, polyimide, polyamideimide, polyetherimide,silicone resin, phenoxy resin, flororesin, liquid crystal polymer, andpolyallylether.

It may be preferable to add to the present resin composition aplasiticizer, a small amount of mold lubricant, a coloring agent, alubricant, a heat resistance stabilizer, a weathering stabilizer, aforming agent, a rust-inhibitor, and a flame retarder.

The present resin composition can be prepared by conventionally knownmethods.

An example of a known method comprises the steps of mixing the PAS resin(A), bisphenol-type epoxy resin (B), and oxazoline-group-containingpolymer (C) and further, if necessary, the impact resistance improvingresin (D) and the other materials homogeneously by a mixer such as atumbler- or a Henschel-type mixer, melting and kneading the mixture attemperatures ranging from 200 to 350° C. by means of a uniaxial orbi-axial extruding and kneading machine, and yielding pellets of thepresent resin composition.

The resin composition of the present invention has a superioradhesiveness with the cured epoxy resin, which is a product of a curingreaction of an epoxy resin and a curing agent.

Examples of the epoxy resins include bisphenol A, bisphenol F, bisphenolS, bisphenol AF, bisphenol AD, 4,4-dihydroxybiphenyl, resorcin,saligenin, trihydroxydiphenyldimethylmethane tetraphenylolmethane, andtheir halogen substitution products and alkyl-group substitutionproducts; glycidylethers synthesized by reacting compounds containingmore than two hydroxygroups such as butanediol, ethyleneglycol,erythrit, novolac, glycerin, and polyoxyalkylene with epichlorohydrin;glycidylesters such as glycidylester phthalate; glycidylaminessynthesized by reacting primary or secondary amines such as aniline,diaminodiphenylmethane, methaxylilenediamine,1,3-bisaminomethylcyclohexane with epichlorohydrin; glycidylepoxy resinof the above compounds, epoxidated soybean oil; and non-glycidylepoxyresins such as vinylcyclohexenedioxide, dicyclopentadienedioxide. Theseepoxy resins are used alone or combinations of two or more.

These epoxy resins are used after cured by the curing agent. Asdescribed earlier, when an epoxy resin is used for sealing variouselements, the epoxy resin is, generally, poured into a casing made ofthe PAS resin after mixed with a curing agent, and the epoxy resin isthen cured by heating or the like. Examples of curing agents includeamines, amino resins, acid anhydrides, polyhydric alcohols, phenolresins, polysulfides, and isocyanates.

The PAS resin compositions of the present invention may be applied notonly semiconductor or electric devices represented by the case of carignition coils applied to the DLI system, but also various applicationswhich require a superior crack resistance property or thermal shockresistance and applications as powder paints, solution-type adhesives,and paints.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a diagram showing an insert-type test piece used forevaluation of Examples 1 to 10 and Comparative Examples 1 to 9, whereinA is a metal (S55C) block, and B is the present resin compositionsprepared by the above Examples.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, practical examples of this application will be described.However, it is to be noted that the present invention is not limited tothese embodiments.

Methods of measuring the terminal thiol concentration, logarithmicviscosity (η), melt flow rate, and total sodium content of PPS obtainedin reference examples are as follows.

(1) Terminal Thiol Concentration:

The same method as the above described “iodoactoamide” method is used.

(2) Logarithmic Viscosity (η):

A relative viscosity of α-methylchloronaphthalene solution of PPS (PPSconcentration is 0.4 g/100 ml) at 206° C. (400° F.) is measured by thefollowing equation.

η=In (relative viscosity)/PPS concentration

(3) Melt Flow Rate:

The melt flow rate is measured according to ASTM D1238, the diameter andthe length of the orifice are 0.0825±0.002 inches and 0.315±0.001inches, respectively, and conditions of the temperature and the load are316° C. and 5000 g respectively.

(4) Total Sodium Content:

The total sodium content is measured by the atomic absorption method forthe polymer after sulfate decomposition.

(5) ΔHCl, ΔNaOH

10 ml of HCl is added to 10 g of the polymer and filtrated afterstirring. The filtrated solid is repeatedly washed by water until no HClis detected (until no white turbidity is detected by dripping of AgNO₃).All of the filtrate used for washing is collected and HCl in thecollected solution is titrated by NaOH, and the molar number of consumedHCl has been defined as ΔHCl.

Subsequently, the polyarylenesulfide resin (A) is re-dispersed indistilled water, and 10 ml of 1 mol/l of NaOH is added and the dispersedsystem is filtrated after stirring. The filtrated solid is repeatedlywashed with water until no NaOH is detected (until no red color isdetected by dripping phenolphtalein). All of the filtrate used forwashing is collected and NaOH in the collected solution is titrated byHCl, and the molar number of consumed NaOH is defined as ΔNaOH.

REFERENCE EXAMPLE 1 Preparation of PPS-1

7,900 g of N-methylpyrrolidone, 3,260 g (25 mol, containing 40% crystalwater) of sodium sulfate, 4.0 g of sodium hydroxide, and 3,400 g (25mol) of sodium acetate trihydyrate were introduced into an autoclavewith a stirrer and the temperature was gradually raised to 205° for twohours in a nitrogen atmosphere, while stirring, and 1500 ml of liquiddistillate including 1.360 g of water was removed.

After the reaction system was cooled to 150° C. 3,750 g (25.5 mol) ofp-dichlorobenzene and 2,000 g of methylpyrrolidone were added and a twostep reaction was conducted at 230° C. for four hours and further at260° C. for two hours.

Subsequently, the autoclave was cooled and the content was separated byfiltration. The cake was then washed by warm water five times, and afterdying, under reduced pressure, granular PPS was yielded (yield of 82%).

Furthermore, approximately 2,200 g of this granular PPS resin was placedinto 20 l of heated water solution of acetic acid of pH4 and 90° C. Thedispersed system was filtrated after stirring for 30 minutes, and thefiltrated solid is washed by deionized water at 90° C. until the pHincreases to 7, and was dried at 120° C. for 24 hours.

The thus obtained PPS resin showed following characteristic values: theterminal thiol concentration is 40 μmol/g, the logarithmic viscosity (η)is 0.32, and the melt flow rate is 100 g/10 min., the total sodiumcontent is 250 ppm, ΔHCl=2.0 μmol/g, and ΔNaOH=20.0 μmol/g. This resinis referred to as PPS-1.

REFERENCE EXAMPLE 2 Preparation of PPS-2

1,993 g of N-methylpyrrolidone, 537 g (4.1 mol) of sodium sulfate 2.7hydrate, 1.6 g (0.04 mol) of sodium hydroxide, and 144 g (1.0 mol) ofsodium benzoate were introduced into an autoclave with a stirrer. Thetemperature was gradually raised to 200° C. or two hours in nitrogenatmosphere while stirring and 102 ml of water was distilled.

After the reaction system was cooled to 105° C., 603 g (4.1 mol) ofp-dichlorobenzene, 1.8 g (0.01 mol) of 1,2,4-trochlorobenzene, and 310 gof N-methylpyrrolidone were added and a two step reaction was conductedat 230° C. for two hours and at 260° C. for three hours. The innerpressure of the autoclave observed was 9.5 Kg/cm² when thepolymerization reaction had completed.

Subsequently, the autoclave was cooled, and the content was separated byfiltration. The obtained cake was washed by heated water three times,and dried after washing by acetone two times and 394 g of light graybrown granular PPS was yielded (yield=89%).

The thus obtained PPS showed following characteristic values: theterminal thiol-group concentration is 15 μmol/g, the logarithmicviscosity (η) is 0.25, the melt flow rate is 550 g/10 min, the totalsodium content is 80 ppm, ΔHCl=10.0 μmol/g, and ΔNaOH=20.0 μmol/g. Thisresin is referred to as PPS-2.

REFERENCE EXAMPLE 3 Preparation of PPS-3

1233 g of methylpyrrolidone, 636 g (5.0 mol, 61.5% by analysis) ofsodium sulfate 2.7 hydrates 510 g (5.0 mol) of lithium acetatedihydrate, and 90 g (5.0 mol) of water were introduced into an autoclavewith a stirrer. 290 ml of liquid distillate including 257 g of water wasgenerated by a reaction at 205° C. for approximately one hour and twentyminutes in a nitrogen atmosphere while stirring.

After the reaction system was cooled to 150° C., a solution of 750 g(5.1 mol) of p-dichlorobenzene in 400 g of N-methylpyrrolidone was addedand a reaction was conducted at 265° C. for three hours. The innerpressure of the autoclave when the reaction had completed was 9.0Kg/min.

Subsequently, the autoclave was cooled to 150° C. and the content wasseparated by filtration. The obtained cake was washed by heated waterthree times, and after washed by acetone two times, the cake wasimmersed in HCl solution of pH 1 at room temperature for 30 min. 467 gof PPS resin was yielded after washing by deionized water and drying at80° C. under reduced pressure (yield=86%).

The thus obtained PPS showed following characteristic values: theterminal thiol-group concentration is 35 μmol/g, the logarithmicviscosity (η) is 0.25, the melt flow rate is 550 g/10 min, the totalsodium content is 100 ppm, ΔHCl=1.0 μmol/g, and ΔNaOH=12.0 μmol/g. Thisresin is referred to as PPS-3.

EXAMPLES 1-10

The PPS resins produced according to respective Reference Examples andrespective combining compounds shown in Tables 1 and 2 were mixedhomogeneously at mixing ratios shown in the same Table and the mixturewas melted and kneaded by means of a biaxial extruder with a diameter of35 mm at 300° C., and pellets were obtained. The properties andcompatibility of those sample pellets were evaluated by use of testpieces which are formed by a three ounce-type injection molding machineunder conditions of the cylinder temperature at 290° C. the moldtemperature at 140° C. the injection pressure of 1,000 Kgf/cm², and amedium injection speed. The results of evaluations were shown in Table 1and 2. A chopped strand glass fiber was used as glass fiber shown inTables 1 and 2.

The following properties were evaluated.

<Mechanical Properties>

(1) Izod Impact Strength

Impact strengths for both notched and non-notched test pieces of ⅛ inchthick, ½ inch wide, and 2.5 inches long were measured according to ASTMD-256. One measured value was obtained by measuring five test pieces.

(2) Crack Resistance Property

Insert-type formed products, each formed by covering a metal (S55C)block A with a resin layer B of 1 ml thick as shown in FIG. 1, weresubjected to a heating and cooling cycle test in vapor phase, in whichone cycle was set “−40° C./one hour ˜40° C./one hour”, and the number ofcycles at which cracks are generated at the outer wall was recorded. Thenumber of test pieces for the test was n=5.

The test results were evaluated by ranks according to the followingrule.

Crack was generated less than 10 cycles . . . “E” rank.

Crack was generated within a range of 10-less than 100 cycles . . . “D”rank.

Crack was generated within a range of 100-less than 300 cycles . . . “C”rank.

Crack was generated within a range of 300-less than 1,000 cycles . . .“B” rank.

Crack was generated more than 1,000 cycles . . . “A” rank.

<Compatibility>

The compatibility was evaluated according to a following standard byvisual inspections of the appearance of sheets having dimensions of 2 mmthick, 50 mm wide, and 100 mm long, using a film gate

◯ . . . the surface of a formed product is smooth and no peeling isobserved;

Δ . . . the surface is uneven and an opal-like gloss is observed;

X . . . the surface of the formed product is uneven and peeling isobserved.

<Dispersed Particle Size of the Impact Resistance Improving Component>

Fractured surfaces of test pieces with notches after testing Izod impactstrength were observed after immersion in heated xylene by a scanningelectron microscope (magnification: 2,500 times).

<Adhesive Strength to the Cured Epoxy Resin>

Test pieces with dimensions of 25 mm wide, 75 mm long and 3 mm thickwere formed by the present resin and an epoxy resin was coated to athickness of 40 to 50 μm on the test piece at a surface area of 25 mm×10mm. After fixing by a clip, the coated layer was cured by treating firstby being maintained at 85° C. for three hours, then being maintained at150° C. for three hours and finally by annealing. The tensile shearingstrength was then measured at a drawing speed of 5 mm/min., and theactual loads were recorded.

The epoxy resin used for measuring the adhesive strength is as follows:

Main component: Epicron 850 (produced by Dainippon Ink & Chemicals Co.Ltd. containing silica) (filling rate: 50 wt %)

Curing agent: hexahydrophthalic acid anhydride

The ratio of the main component/curing agent=100/30.

<Epoxy-potting Material Adhesive Strength>

A box-shaped product with a base of 30 mm in width and 80 mm in lengthand with a height of 15 mm and a wall thickness of 2 mm is formed, andthe same epoxy resin used for measuring adhesive strength was poured tothe height of 10 mm, and cured under the same conditions. The heatingand cooling cycle tests were executed in a gas phase by repeating thecycles of “−40° C./one hour −140° C./one hour”, and the number of cyclesuntil peeling occurs at the interface between the inner surface of thebox-shaped product and the cured epoxy resin was recorded.

The evaluation was carried out by ranking the number of cycles asfollows.

Peeling was caused less than 10 cycles: rank IV

Peeling was caused in a range equal to or more than 10 to less than 100cycles . . . rank “III”.

Peeling was caused in a range equal to or more than 100 to less than 300cycles . . . rank “II”.

Peeling was caused equal to or more than 300 cycles . . . “I”.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 PPS resinPPS-1 (80) PPS-1 (77) PPS-1 (70) PPS-2 (50) PPS-3 (55) Epoxy resin B-1(2) B-1 (5) B-2 (6.5) B-2 (3) B-1 (10) Oxazoline-type resin C-1 (15) C-1(3) C-2 (12) C-2 (12) C-2 (10) Impact resistance D-1 (3) D-2 (15) D-3(10) D-4 (15) D-5 (5) improving rein Glass fiber — — — (20) (20) Silanecompounds — — F-1 (1) — — G component — — G-1 (1) — — Impact strengthJ/m With notch: without notch 120 200 160 130 100 Crack resistance900 >2,000 >2,000 600 640 property B B B A A Compatibility ∘ ∘ ∘ ∘ ∘Gum-particle size: 0.5-0.8 <0.5 0.5-0.8 <0.5 0.5-0.8 μm Adhesivestrength, 180 155 195 215 230 Adherence II II II I I

TABLE 2 Example 6 Example 7 Example 8 Example 9 Example 10 PPS resinPPS-3 (66) PPS-3 (60) PPS-3 (53) PPS-2 (45) PPS-3 (40) Epoxy resin B-1(6) B-1 (5) B-1 (5) B-1 (3) B-2 (2) Oxazoline-type resin C-1 (2) C-1(7.7) C-1 (6.7) C-2 (6) C-2 (3.5) Impact resistance D-6 (6) D-2 (6) D-7(4) D-8 (4.5) D-1 (3) improving rein Glass fiber (20) (20) (30) (40)(50) Silane compounds — F-1 (1) F-1 (1) F-2 (1) F-3 (1) G component —G-2 (0.3) G-3 (0.3) G-2 (0.5) G-3 (0.5) Impact strength J/m With notch:without notch 110 110 100 95 85 Crack resistance 700 720 750 750 720property A A A A A Compatibility ∘ ∘ ∘ ∘ ∘ Gum-particle size: 0.5-0.8<0.5 <0.5 0.5-0.8 0.5-0.8 μm Adhesive strength, 190 250 240 230 200Adherence I I I I I

COMPARATIVE EXAMPLES 1 to 9

The PPS resins produced according to respective Reference Examples andrespective combining compounds shown in Tables 3 and 4 were mixedhomogeneously at mixing ratios shown in the same Table and the mixturewas melted and kneaded by means of a biaxial extruder at 300° C. andpellets were obtained. The same properties as those for Examples 1 to 10were evaluated. The results were shown in Tables 3 and 4.

TABLE 3 Comparative Comparative Comparative Comparative ComparativeExample 1 Example 2 Example 3 Example 4 Example 5 PPS resin PPS-1 (77)PPS-1 (77) PPS-1 (70) PPS-2 (65) PPS-3 (65) Epoxy resin B-3 (5) B-4 (5)B-2 (6.5) B-2 (3) — Oxazoline-type — C-1 (3) C-2 (12) C-2 (12) C-2 (10)resin Impact resistance D-2 (15) D-2 (15) D-9 (10) — D-5 (5) improvingrein Glass fiber — — — (20) (20) Silane compounds — — F-1 (1) — — Gcomponent — — G-1 (1) — — Impact strength J/m With notch: 45 50 45 35 68without notch 380 400 380 350 470 Crack resistance E E E E E propertyCompatibility x x x ∘ Δ Gum-particle size: 1.0-2.0 1.0-2.0 1.0-2.0 —1.0-2.0 μm Adhesive strength, 75 70 80 85 70 Adherence IV IV IV IV IV

TABLE 4 Com- Com- Comparative Comparative parative parative Example 6Example 7 Example 8 Example 9 PPS resin PPS-3 (66) PPS-3 (58) PPS-2PPS-3 (51) (78) Epoxy resin B-1 (6) — B-1 (3) — Oxazoline-type — — — —resin Impact resistance D-6 (6) D-3 (10) D-3 (4.5) — improving resinGlass fiber (20) (30) (40) (20) Silane — — F-2 (1) F-2 (1) compounds Gcomponent — — — G-2 (1) Amide-type wax — (2) (0.5) — Impact strength J/mWith notch: 60 70 72 25 without notch 440 480 490 280 Crack resistance EE E E property Compatibility Δ Δ Δ ∘ Gum-particle size: 1.0-2.0 1.0-2.01.0-2.0 — μm Adhesive strength, 85 90 95 68 Adherence IV IV IV IV

In Tables 1 to 4, numeral values in parentheses represent weight %, andG components represent the ester of the higher fatty acid ester ofpolyhydric alcohol. Abbreviations in those tables indicate followingcompounds.

B-1: bisphenol A-type epoxy resin, epoxy equivalent 2,000;

B-2: bisphenol A-type epoxy resin, epoxy equivalent 190;

B-3: bisphenol S-type epoxy resin, epoxy equivalent 210 (Trade name:Epicron EXA-1514, produced by Dainippon Ink and Chemicals Inc.);

B-4: epoxidated product of 1,6-dihydroxynaphthalene, epoxy equivalent150 (Trade name: Epicron XP4032, produced by Dainippon Ink and ChemicalsInc.).

The above compounds are bisphenol A-type epoxy resin (B).

C-1: oxazoline containing 5 wt % of vinyloxazoline/styrene copolymer;

C-2: oxazoline containing 5 wt % of vinyloxazoline/styrene/acrylonitrilecopolymer, styrene/acrylonitrile=70/25.

The above compounds are oxazoline-group-containing polymer (C).

D-1: maleic acid anhydride (Maah)-graft-ethylene (Et); and propylene(PP) copolymer, Et/PP/Maah=58/40/2.

D-2: ethylene/ethylacrylate (EA)/maleic acid anhydride ternary copolmer,Et/EA/Maah=66/32/2.

D-3: ethylene/glycidylmethacrylate (GMA) copolymer, Et/GMA=88/12.

D-4: ethylene/ethylacrylate/glycidylmethacrylate ternary copolymer,Et/EA/GMA=68/24/8.

D-5: maleic anhydride-graft-styrene/butadiene/styrene block hydrogenatedcopolymer, ethylene-butene/styrene/Maah=68/30/2.

D)-6: GMA copolymerized styrene/butadiene/styrene block hydrogenatedcopolymer, ethylene-butane/styrene/GMA=68/30/2.

D-7: ethylacrylate/butylacrylate (BA)/maleic acid anhydride copolymer,EA/BA/Maah=62/36/2.

D-8: ethylacrylate/butylacrylate (BA)/glycidylmethacrylate copolymer,EA/BA/GMA=62/36/2=68/30/2.

D-9: ethylene/ethylacrylate (EA) copolymer, Et/EA=85/15.

The above compounds are impact resistance improving resins (D).

F-1: γ-glycidoxypropyltrimethoxysilane;

F-2: γ-aminopropyltriethoxysilane;

F-3: isocyanatepropyltriethoxysilane.

The above compounds are silane compounds (F).

G-1: ethyleneglycoldimontanate;

G-2: tromethylolpropanetrimontanate;

G-3: pentaerythritoltetrastearate.

The above compounds are esters of higher fatty acid of polyhydricalcohol.

The other components:

Amide-type wax; and amidecarboxylate-type wax which is a reactionproduct of stearic acid, sebacic acid, and ethylenediamine (anendothermic peak by the DSC measurement appeared at 143° C.), andcontent of ethylenebisstearylamide is 30%.

According to the present invention, it becomes possible to improvedramatically the adhesive strength of the PAS resin to the cured epoxyresin, and to improve dramatically the crack resistance property of thePAS resin when subjected to heating and cooling cycles by the use of animpact resistance improving resin.

Accordingly, the resin compositions of the present invention can be usedas superior engineering plastics in wide application fields such aselectronic and other devices.

What is claimed is:
 1. A resin composition comprising (A) apolyarylenesulfide resin, (B) a bisphenol epoxy resin, (C) an oxazolinegroup-containing amorphous polymer, and (D) an impactresistance-improving resin, wherein said impact resistance improvingresin (D) is a resin component selected from the group consisting ofvinylpolymer (d1) containing acid or epoxy groups and gum polymers (d2)containing acid or epoxy groups.
 2. A resin composition according toclaim 1, wherein said composition further comprises a fibrousreinforcing material (E) in addition to said components (A) to (D).
 3. Aresin composition according to claim 1, wherein said polyarylenesulfideresin (A) is a resin having characteristic values, such that ΔHCl is notmore than 10 μmol/g, ΔNaOH is in a range of 5 to 30 μmol/g, and(ΔNaOH-ΔHCl) ≧5 μmol/g.
 4. A resin composition according to claim 3,wherein said polyarylenesulfide resin (A) has more than 70 mol % of astructural unit expressed by the following chemical formula (1)


5. A resin composition according to claim 1, wherein said vinyl polymerscontaining acid or epoxy groups is an α-polyolefin (d1-1) containingacid or epoxy groups.
 6. A resin composition according to claim 5,wherein said α-polyolefin (d1-1) containing acid or epoxy groups is acopolymer of an α-olefin, an α,β-unsaturated carboxylic acid or itsanhydride, and an α,β-unsaturated alkylester carboxylate.
 7. A resincomposition according to claim 1, wherein said vinyl polymer (d1)containing acid or epoxy groups is α,β-unsaturated alkylestercarboxylate polymer (d1-1) containing acid or epoxy groups.
 8. A resincomposition according to claim 1, wherein said gum polymer (d2)containing acid or epoxy groups is a hydrogenated product of a copolymerof a conjugated diene and aromatic vinyl monomer containing acid orepoxy groups.
 9. A resin composition according to claim 1, wherein saidoxazoline group containing amorphous polymer (C) is a copolymercomprised of vinyloxazoline and styrene monomers.
 10. A resincomposition according to claim 1, wherein said resin composition furthercomprises a silane compound.
 11. A resin composition according to claim1, wherein said resin composition further comprises a higher fatty acidester of a polyhydric alcohol.